JP2006083284A - Polyolefin-based resin composition and easily disintegrable moisture-proof paper comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyolefin-based resin composition providing very easily disintegrable properties and enabling extrusion-lamination processing to be carried out. <P>SOLUTION: The polyolefin-based resin composition is obtained by compounding (A) 99.9-50 wt.% polyethylene-based resin satisfying the following requirements (a) to (d), with (B) 0.1-50 wt.% polyolefin-based wax satisfying one requirement in the following requirements (e) to (g): (a) having ≥890 kg/m<SP>3</SP>and ≤980 kg/m<SP>3</SP>density; (b) having ≥6C long chain branches of not less than 0.01 and not more than 3 per 1,000 carbon atoms; (c) satisfying both of expressions (1) and (2): MS<SB>190</SB>>22×MFR<SP>-0.88</SP>(1) and MS<SB>160</SB>>110-110×log (MFR) (2); (d) having only one peak in an endothermic curve; (e) having ≥100 and ≤10,000 M<SB>n</SB>; (f) having ≥200 and ≤20,000 M<SB>w</SB>and (g) having ≥200 and ≤20,000 M<SB>h</SB>. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyolefin resin composition and a disaggregating moisture-proof paper using the same.

  The moisture-proof wrapping paper is obtained by extrusion laminating a branched low density polyethylene (LDPE) on a paper substrate such as kraft paper. However, in recent years, moisture-proof paper having excellent disaggregation properties has been demanded from the viewpoint of paper recycling. In order to excel in disaggregation, it is necessary to cut not only the paper but also the coating material to some extent during stirring in the pulper. Therefore, it is difficult with conventional moisture-proof wrapping paper composed of LDPE and paper. Met. Then, although the method of coating the emulsion latex etc. excellent in the disaggregation property is proposed, it is a big subject that it is inferior to cost performance and the drying equipment of a coating liquid is required. In addition, moisture-proof paper is also proposed in which amorphous polyolefin is coated with a moisture-proof thermoplastic resin composition mainly composed of a tackifying resin and a wax (see, for example, Patent Documents 1 and 2). The moisture-proof paper obtained by such a method has the advantage of being excellent in moisture resistance and disaggregation. However, since amorphous polyolefin used as the main component is amorphous and soft, it tends to cause tackiness on moisture-proof paper. there were.

JP-A-9-316252 JP, 11-158330, A Also, a method of blending a low molecular weight low density polyethylene with a tackifier and a wax and molding by extrusion coating (for example, see Patent Document 3), ethylene-vinyl acetate copolymer resin, amorphous A method of blending a water-soluble polypropylene resin, a tackifier and a wax and extrusion coating (for example, see Patent Document 4), a method of blending polyethylene and / or polypropylene, a tackifier resin and a wax and extrusion coating (for example, Although Patent Document 5) has been proposed, since it contains a tackifier resin, it has a poor problem of molding processability, and tack is likely to occur.

JP 2004-26885 A JP 2001-164217 A Japanese Patent Laid-Open No. 2002-3660

  The present invention has been made in order to solve the above-described problems of the prior art, and is suitable for moisture-proof paper having excellent disaggregation properties without mixing a tackifying resin, and is a polyolefin-based resin composition that can be extrusion laminated. It provides things.

The present invention has been found as a result of intensive studies on the above-described object. That is, the present invention relates to a polyethylene-based resin (A) that satisfies the following requirements (a) to (d) (99.9 to 50% by weight) and a polyolefin-based wax that satisfies any of the following requirements (e) to (g): (B) The present invention relates to a polyolefin resin composition comprising 0.1 to 50% by weight.
(A) The density is 890 kg / m ³ or more and 980 kg / m ³ or less,
(B) The number of long chain branches having 6 or more carbon atoms is 0.01 to 3 per 1,000 carbon atoms,
(C) Melt tension (MS ₁₉₀ ) (mN) measured at 190 ° C. and MFR (g / 10 min, 190 ° C.) with a load of 2.16 kg are expressed by the following formula (1)
MS ₁₉₀ > 22 × MFR ^−0.88 (1)
The melt tension (MS ₁₆₀ ) (mN) measured at 160 ° C. and the MFR (g / 10 min, 190 ° C.) with a load of 2.16 kg satisfy the following formula (2),
MS ₁₆₀ > 110-110 × log (MFR) (2)
(D) the peak of an endothermic curve obtained in the measurement Atsushi Nobori by a differential scanning calorimeter is one (e) number average molecular weight measured by gel permeation chromatography (M _n) of 100 to 10,000,
(F) The weight average molecular weight (M _w ) measured by gel permeation chromatography is 200 or more and 20,000 or less,
(G) The viscosity average molecular weight (M _h ) measured by the viscosity method is 200 or more and 20,000 or less, and the present invention will be described in detail.

The density of the polyethylene resin (A) used in the present invention is 890 kg / m ³ or more and 980 kg / m ³ or less, preferably 940 kg, as a value measured by a density gradient tube method in accordance with JIS K6922-1 (1998). / ^{m 3} or more 980 kg / ^{m 3} or less, more preferably 951Kg / ^{m 3} or more 980 kg / ^{m 3} or less. If the density is less than 890 kg / m ³ , the resulting resin composition may be highly tacky, and if it exceeds 980 kg / m ³ , it takes a long time for crystal melting, which may result in inferior moldability. In particular, in the case of using the resin composition of the present invention to EkiHanare disintegrable moistureproof paper, and 951kg / m ³ or more 980 kg / m ³ or less the density of the polyethylene resin (A) since the excellent defibration properties can be obtained It is preferable.

The number average molecular weight (M _n ) in terms of linear polyethylene of the polyethylene-based resin (A) used in the present invention is greater than 10,000 and 1,000,000 or less, preferably 20,000 or more and 700,000. Or less, more preferably 25,000 or more and 300,000 or less. If _Mn is 10,000 or less or exceeds 1,000,000, it may be extremely difficult to perform molding. Moreover, the weight average molecular weight ( _Mw ) of the linear polyethylene conversion of the polyethylene-type resin (A) used for this invention is more than 20,000 and below 2,000,000, Preferably it is 25,000 or more and 1 000,000 or less, more preferably 30,000 or more and 600,000 or less. If _Mw exceeds 20,000 or exceeds 2,000,000, it may be extremely difficult to perform the molding process. M _n and M _w are measured by gel permeation chromatography (GPC).

  The MFR at 190 ° C. and 2.16 kg load of the polyethylene resin (A) used in the present invention is 0.01 to 300 g / 10 minutes, preferably 1 to 200 g / 10 minutes, more preferably 20 to 150 g / 10 minutes. It is. If the MFR is less than 0.01 g / 10 min or exceeds 300 g / 10 min, molding may be difficult. Moreover, when using the resin composition of this invention for easily disintegrable moisture-proof paper, it is preferable that it is 20-150 g / 10min from the outstanding disintegration property being acquired.

The number of long-chain branches of the polyethylene resin (A) used in the present invention is 0.01 or more and 3 or less per 1,000 carbon atoms. The molding process can be performed satisfactorily. The number of long-chain branches is the number of branches of hexyl groups or more (6 or more carbon atoms) detected by ¹³ C-NMR measurement.

The melt tension MS ₁₉₀ (mN) measured at 190 ° C. of the polyethylene-based resin (A) used in the present invention and the MFR (g / 10 min, 190 ° C.) with a load of 2.16 kg are represented by the following formula (1).
MS ₁₉₀ > 22 × MFR ^−0.88 (1)
Preferably, the following formula (1) ′
MS ₁₉₀ > 30 × MFR− ^0.88 (1) ′
More preferably, the following formula (1) "
MS ₁₉₀ > 7 + 30 × MFR ^−0.88 (1) ”
It is in the relationship shown by. If the formula (1) is not satisfied, the moldability may be inferior.

The melt tension MS ₁₆₀ (mN) measured at 160 ° C. and the MFR (g / 10 min, 190 ° C.) with a load of 2.16 kg of the polyethylene-based resin (A) used in the present invention are expressed by the following formula (2).
MS ₁₆₀ > 110-110 × log (MFR) (2)
Preferably, the following formula (2) ′
MS ₁₆₀ > 195-110 × log (MFR) (2) ′
More preferably, the following formula (2) "
MS ₁₆₀ > 205-110 × log (MFR) (2) ”
It is in the relationship shown by. If the formula (2) is not satisfied, the moldability may be inferior.

  The polyethylene-based resin (A) used in the present invention has one endothermic curve peak obtained by temperature rise measurement using a differential scanning calorimeter (DSC), and the resin composition obtained thereby has The temperature dependence of the elastic modulus is small and the heat resistance is excellent. The endothermic curve is obtained by inserting 5 to 10 mg of sample into an aluminum pan and raising the temperature with DSC. Note that the temperature rise measurement is performed by previously leaving at 230 ° C. for 3 minutes, then lowering the temperature to −10 ° C. at 10 ° C./min, and then raising the temperature to 150 ° C. at a rate of 10 ° C./min .

The polyethylene resin (A) used in the present invention has a shrinkage factor (g ′ value) evaluated by GPC / intrinsic viscometer of 0.1 or more and less than 0.9, and further 0.1 or more and 0.7 or less. It is preferable because the resin composition obtained has excellent moldability. The shrinkage factor (g ′ value) in the present invention is a parameter representing the degree of long-chain branching, and the intrinsic viscosity of the polyethylene-based resin at an absolute molecular weight three times the weight average molecular weight (M _w ) is completely different from the branching. It is the ratio of the intrinsic viscosity at the same molecular weight of no high density polyethylene (HDPE). Further, the relationship between the g ′ value and the contraction factor (g value) evaluated by the GPC / light scatterometer is preferably the formula (3), more preferably the formula (3) ′. As a result, the moldability is further improved. In addition, g value is a ratio of the root mean square of the inertial radius of this polyethylene-type resin in the absolute molecular weight 3 times _Mw , and the mean square of the inertial radius in the same molecular weight of HDPE without a branch.

0.2 <log (g ′) / log (g) <1.3 (3)
0.5 <log (g ′) / log (g) <1.0 (3) ′
Further, between the g value in an absolute molecular weight three times the _{M w (g 3M)} and g values of the absolute molecular weight of 1 × _{M w (g M),} formula (4), preferably of formula (4) ' More preferably, the relationship represented by the formula (4) "is desirable from the viewpoint of moldability.

0 <g _3M / g _M ≦ 1 (4)
0 <g _3M / g _M ≦ 0.9 (4) ′
0 <g _3M / g _M ≦ 0.8 (4) ”
The polyethylene-based resin (A) used in the present invention has an ethylene polymer having a vinyl group at the terminal obtained by polymerizing ethylene, or a terminal obtained by copolymerizing ethylene and an olefin having 3 or more carbon atoms. An ethylene copolymer having a vinyl group,
(H) M _n is 2,000 or more,
(I) It is desirable to be obtained by polymerizing ethylene and optionally an olefin having 3 or more carbon atoms in the presence of a macromonomer having M _w / M _n of 2 or more and 5 or less. The macromonomer is an olefin polymer having a vinyl group at the terminal, preferably an ethylene polymer having a vinyl group at the terminal obtained by polymerizing ethylene, or copolymerizing ethylene and an olefin having 3 or more carbon atoms. The ethylene copolymer having a vinyl group at the terminal obtained by the above method, more preferably long chain branching (i.e., ¹³ C-NMR among branches other than the branch derived from olefin having 3 or more carbon atoms, which is optionally used). Linear ethylene polymer or linear ethylene copolymer having a vinyl group at the terminal, wherein the number of branches of hexyl groups detected by measurement is less than 0.01 per 1,000 main chain methylene carbons It is.

  Examples of the olefin having 3 or more carbon atoms include propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, α-olefin such as vinylcycloalkane, norbornene, Examples include cyclic olefins such as norbornadiene, dienes such as butadiene or 1,4-hexadiene, and styrene. Two or more of these olefins can be mixed and used.

When an ethylene polymer having a vinyl group at the terminal or an ethylene copolymer having a vinyl group at the terminal is used as the macromonomer, the linear polyethylene equivalent number average molecular weight (M _n ) is 2,000 or more. , Preferably it is 3,000 or more, More preferably, it is 5,000 or more. The weight average molecular weight (M _w ) in terms of linear polyethylene is 3,000 or more, preferably 5,000 or more, and more preferably greater than 10,000. The ratio of the weight average molecular weight (M _w ) to M _n (M _w / M _n ) is 2 or more and 5 or less, preferably 2 or more and 4 or less, more preferably 2 or more and 3.5 or less. . The following general formula (5)
Z = [X / (X + Y)] × 2 (5)
(Where X is the number of vinyl ends per 1,000 main chain methylene carbons of the macromonomer, and Y is the number of saturated ends per 1,000 main chain methylene carbons of the macromonomer.)
The ratio (Z) between the number of vinyl ends and the number of saturated ends represented by is from 0.25 to 1, preferably from 0.50 to 1. X and Y are determined by ¹ H-NMR, ¹³ C-NMR, FT-IR, or the like. For example, in ¹³ C-NMR, the presence and amount of vinyl end can be confirmed by peaks at 114 ppm and 139 ppm at the vinyl end and 32.3 ppm, 22.9 ppm and 14.1 ppm at the saturated end.

  The production method of the macromonomer in the present invention is not particularly limited, but when producing an ethylene polymer having a vinyl group at the terminal or an ethylene copolymer having a vinyl group at the terminal as the macromonomer, for example, Group 3 of the periodic table A method of polymerizing ethylene using a catalyst containing a metallocene compound containing a transition metal selected from Group 4, Group 5 and Group 6 as a main component can be used. Examples of the cocatalyst include organoaluminum compounds, proton acid salts, Lewis acid salts, metal salts, Lewis acids and clay minerals.

  The polyethylene resin used in the present invention is a macromonomer using, for example, a catalyst containing as a main component a metallocene compound containing a transition metal selected from Group 3, Group 4, Group 5 and Group 6 of the periodic table. Is obtained by polymerizing ethylene and optionally an olefin having 3 or more carbon atoms. Moreover, a cocatalyst can be used similarly to manufacture of a macromonomer. The polymerization temperature is in the range of -70 to 300 ° C, preferably 0 to 250 ° C, more preferably 20 to 150 ° C. The ethylene partial pressure is in the range of 0.001 to 300 MPa, preferably 0.005 to 50 MPa, and more preferably 0.01 to 10 MPa. Further, hydrogen may be present as a molecular weight regulator in the polymerization system.

  In the present invention, when ethylene and an olefin having 3 or more carbon atoms are polymerized in the presence of a macromonomer, the ethylene / olefin having 3 or more carbon atoms (molar ratio) is 1 to 200, preferably 3 to 100, and more preferably. 5 to 50 can be used.

  The polyolefin wax (B) used in the present invention is not particularly limited, and one or two or more of linear or branched polyethylene wax, ethylene / vinyl acetate copolymer wax, polypropylene wax and the like are used in combination. .

The molecular weight of the polyolefin wax (B) used in the present invention is characterized by satisfying any of the following (e) to (g), and the resin composition obtained by being in this range exhibits excellent disaggregation properties. .
(E) The number average molecular weight (M _n ) measured by gel permeation chromatography is 100 or more and 10,000 or less,
(F) The weight average molecular weight (M _w ) measured by gel permeation chromatography is 200 or more and 20,000 or less,
(G) The viscosity average molecular weight (M _h ) measured by the viscosity method is 200 or more and 20,000 or less.

  In addition, the method of calculating | requiring a viscosity average molecular weight is described in the following literature, for example.

Okamura et al., “Introduction to Polymer Chemistry”, 2nd edition, p. 63, Chemical Doujin, 1981.
Ikeno et al., “Molecular Weight of Polymers”, p. 7, Kyoritsu Publishing, 1992.
The mixing ratio of the polyethylene resin (A) and the polyolefin wax (B) is (A) / (B) = 99.9 / 0.1-50 / 50 (% by weight), preferably (A) / (B ) = 90 / 10-60 / 40 (wt%). When the ratio of the polyethylene resin (A) exceeds 99.9% by weight, the cutting property of the resin composition is inferior, and when used for moisture-proof paper, the disaggregation is inferior. Further, when the ratio of the polyethylene resin (A) is less than 50% by weight, the molding process becomes difficult.

  The mixing method of the polyethylene resin (A) and the polyolefin wax (B) is arbitrary, and includes a melt mixing method and a dry blend method in which pellets of the polyethylene resin (A) and the polyolefin wax (B) are mixed in a solid state. Either is acceptable. However, the melt mixing method is preferred when quality stability is required. Melt mixing is performed by, for example, an internal mixer such as a Banbury mixer, a batch mixer such as a pressure kneader or a roll kneader, or a continuous mixer such as a single-screw / double-screw extruder. The mixing temperature is not particularly limited as long as it is equal to or higher than the melting point of the polyethylene resin (A). However, in order to suppress thermal deterioration and obtain a resin composition having a stable quality, the mixing temperature is 150 ° C. or higher and 250 ° C. or lower. Is desirable.

  The resin composition of the present invention has an MFR at 190 ° C. and a load of 2.16 kg of 0.01 g / 10 min or more and 300 g / 10 min or less, preferably 1 g / 10 min or more and 200 g / 10 min or less, more preferably 30 g / 10. Min. To 180 g / 10 min. If the MFR is less than 0.01 g / 10 min or exceeds 300 g / 10 min, the moldability is inferior. Moreover, when using the resin composition of this invention for an easily disintegratable moisture-proof paper, it is preferable that they are 30 g / 10min or more and 180 g / 10min or less. If the MFR is less than 30 g / 10 minutes, the disintegration property is poor, and if it exceeds 180 g / 10 minutes, extrusion lamination may be difficult.

  When the resin composition of the present invention is used for easily disintegratable moisture-proof paper, the tensile elongation at break measured by JIS K6922-2 is preferably 10% or less. When it exceeds 10%, the disaggregation property is inferior. The tensile test piece is obtained by punching a compression test piece having a thickness of 1 mm with a punching blade, and has a value measured at 23 ° C.

  The resin composition of the present invention includes a heat stabilizer, weather stabilizer, antistatic agent, antifogging agent, antiblocking agent, slip agent, lubricant, nucleating agent, pigment, carbon black, talc, glass powder, glass fiber, etc. Known additives such as inorganic fillers or reinforcing agents, organic fillers or reinforcing agents, flame retardants, and neutron shielding agents can be blended. Moreover, it can also be used by mixing with other thermoplastic resins. Examples of these include HDPE, linear low density polyethylene (L-LDPE), LDPE, polypropylene resin, poly-1-butene, poly-4-methyl-1-pentene, ethylene / vinyl acetate copolymer, ethylene -A vinyl alcohol copolymer, polystyrene, these maleic anhydride graft products, etc. can be illustrated.

The resin composition of the present invention is shaped by various molding methods such as injection, compression, extrusion, film, extrusion lamination, blow, calendar, transfer, sheet, spinning, and foaming. Further, secondary processing can be performed by a dry laminating method, a thermoforming method, heat sealing, or the like. In particular, since it is excellent in extrusion laminate moldability, it can be laminated on various substrates. When performing extrusion laminate molding, any of single laminate, tandem laminate, coextrusion laminate, and sandwich laminate may be used, and there is no particular limitation. Moreover, when performing an extrusion lamination process, in order to improve the adhesiveness of a base material and the resin composition of this invention, it is preferable to extrude from a die | dye at the temperature of 250-350 degreeC. Moreover, when extrusion laminating the resin composition of the present invention, at least the surface of the molten film that contacts the substrate is preferably oxidized with air or ozone gas from the viewpoint of improving substrate adhesion. When the oxidation reaction with air proceeds, it is preferable to extrude from a die at a temperature of 270 ° C. or higher, and when the oxidation reaction with ozone gas proceeds, it is preferable to extrude at 250 ° C. or higher. In addition, it is preferable that the processing amount of ozone gas is 0.5 mg or more per 1 m ^{2 of} the film extruded from the die. Moreover, in order to improve adhesiveness with a base material, you may perform well-known surface treatments, such as an anchor-coat agent process, a corona discharge process, a flame process, and a plasma process, to the adhesion surface of a base material. Examples of the substrate include synthetic polymer film and sheet, woven fabric, non-woven fabric, metal foil, paper, cellophane and the like. For example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polylactic acid, polyamide resins such as nylon 6, nylon 66 and nylon 12, HDPE, L-LDPE, LDPE, ethylene / ethyl acrylate copolymer, ethylene / methacrylic Acid copolymers, ethylene / vinyl acetate copolymers, ethylene / vinyl alcohol copolymers, polyethylene resins such as ionomers, polypropylene resins, polybutene, acrylic resins, polyvinyl alcohol, polymethylpentene, polyvinyl chloride, poly Examples thereof include films and sheets made of synthetic polymer such as vinylidene chloride, polystyrene, polycarbonate, polyurethane, and cellulose resin. Further, these polymer films and sheets may be further subjected to aluminum vapor deposition, alumina vapor deposition, silicon dioxide vapor deposition, or acrylic treatment. Further, these polymer films and sheets may be further printed using urethane-based ink or the like. Examples of the metal foil include aluminum foil and copper foil, and examples of the paper include kraft paper, fine paper, stretched paper, glassine paper, board paper such as cup base paper and photographic paper base paper. In particular, in order to obtain easily disintegratable moisture-proof paper, it is preferable to carry out extrusion lamination on kraft paper, and it is preferable to perform corona discharge treatment on the surface of kraft paper. In the easily disintegratable moisture-proof paper, the resin composition of the present invention is coated with a thickness of 1 μm to 100 μm, preferably 3 μm to 30 μm, more preferably 5 μm to 20 μm. If it is less than 1 μm, the moisture resistance may be impaired, and if it exceeds 100 μm, the disintegration property may be inferior.

  The resin composition of the present invention is a dry food such as snack confectionery, instant noodles, soup, miso, pickles, sauces, aquatic food and beverage packaging such as beverages, medicines, pharmaceutical products such as infusion bags, shampoos, cosmetics, diapers To be used as a wide range of films, containers, tapes, supports, such as toiletries such as backsheets, photographic paper supports, paper cups and lids, release papers and release tapes, easy-release films, and semi-retort packs made of paper it can. In particular, it is preferably used for easily disintegratable moisture-proof paper.

  The polyolefin resin composition of the present invention is excellent in moisture resistance and exhibits excellent disaggregation properties, and is therefore preferably used for easily disintegratable moisture-proof paper.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

  Preparation of modified hectorite, preparation of a catalyst for producing a macromonomer, production of a macromonomer, production of polyethylene and solvent purification were all carried out under an inert gas atmosphere. As the preparation of modified hectorite, the preparation of a catalyst for producing a macromonomer, the production of a macromonomer, the solvent used for the production of polyethylene, all of the solvents previously purified, dried and deoxygenated in a known manner were used. Dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, diphenylmethylene (1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2,7-di-t-butyl-9 -Fluorenyl) zirconium dichloride was synthesized and identified by a known method. Tosoh Finechem Co., Ltd. has a hexane solution of triisobutylaluminum (0.714M), a toluene solution of methylalumoxane (trade name: PMAO; Al: 2.4 mol / L) and a toluene solution of triisobutylaluminum (0.848M). ) Was used.

  Furthermore, various physical properties of the polyethylene resins in Examples and Comparative Examples were measured by the methods shown below.

-Molecular weight and molecular weight distribution-
The weight average molecular weight (M _w ) and number average molecular weight (M _n ) were measured by gel permeation chromatography (GPC). Tosoh Co., Ltd. HLC-8121GPC / HT is used as the GPC device, Tosoh Co., Ltd. TSKgel GMHhr-H (20) HT is used as the column, the column temperature is set to 140 ° C., and 1 is used as the eluent. The measurement was performed using 2,4-trichlorobenzene. A measurement sample was prepared at a concentration of 1.0 mg / mL, and 0.3 mL was injected and measured. The calibration curve of molecular weight is calibrated using a polystyrene sample having a known molecular weight. In addition, _Mw and _Mn were calculated | required as a value of linear polyethylene conversion.

-Contraction factor (g 'value)-
The shrinkage factor (g ′ value) is the [η] at 3 times the absolute molecular weight of _Mw determined by the method of measuring [η] of polyethylene resin fractionated by GPC, at the same molecular weight of HDPE without any branching. The value divided by [η]. Tosoh Co., Ltd. HLC-8121GPC / HT is used as the GPC device, Tosoh Co., Ltd. TSKgel GMHhr-H (20) HT is used as the column, the column temperature is set to 145 ° C., and 1 is used as the eluent. Measurement was performed using 2,4-trichlorobenzene. A measurement sample was prepared at a concentration of 2.0 mg / mL, and 0.3 mL was injected and measured. As a viscometer, a capillary differential pressure viscometer 210R + manufactured by Viscotek was used.

~ Shrink factor (g value) ~
The shrinkage factor (g value) was determined by a method of measuring the radius of inertia of a polyethylene resin fractionated by GPC by light scattering. This is a value obtained by dividing the root mean square of the radius of inertia at an absolute molecular weight of 3 times _Mw of the polyethylene resin used in the present invention by the root mean square of the same molecular weight of HDPE having no branching. As the light scattering detector, a multi-angle light scattering detector DAWV EOS manufactured by Wyatt Technology was used, and the wavelength of 690 nm was 29.5 °, 33.3 °, 39.0 °, 44.8 °, 50.7. °, 57.5 °, 64.4 °, 72.3 °, 81.1 °, 90.0 °, 98.9 °, 107.7 °, 116.6 °, 125.4 °, 133.2 Measurements were made at detection angles of °, 140.0 °, and 145.8 °.

~ Z value ~
The terminal structure of a macromonomer such as a vinyl terminal or a saturated terminal was measured by ¹³ C-NMR using a JNM-ECA400 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd. The solvent is tetrachloroethane -d _2. The number of vinyl ends was determined from the average value of peaks at 114 ppm and 139 ppm as the number per 1,000 main chain methylene carbons (chemical shift: 30 ppm). Similarly, the number of saturated terminals was determined from the average value of peaks at 32.3 ppm, 22.9 ppm, and 14.1 ppm. From this vinyl terminal number (X) and saturated terminal number (Y), Z = [X / (X + Y)] × 2 was determined.

~density~
The density was measured by a density gradient tube method according to JIS K6922-1 (1998).

~ MFR ~
MFR was measured at 190 ° C. under a load of 2.16 kg in accordance with JIS K6922-1 (1998).

~ Number of long chain branches ~
The number of long chain branches of the polyethylene resin was measured by ¹³ C-NMR using a JNM-GSX270 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd.

~ Melting tension ~
The melt tension (MS) of the polyethylene resin is 8 mm in length (L) and 2.095 mm in diameter (D) into a capillary viscometer (Toyo Seiki Seisakusho, trade name: Capillograph) with a barrel diameter of 9.55 mm. Measurement was performed by mounting a die having a 90 ° angle. For MS, the temperature was set to 160 ° C. or 190 ° C., the piston lowering speed was set to 10 mm / min, the stretch ratio was set to 47, and the load (mN) required for take-up was MS.

~ Number of endothermic peaks ~
Measurement was performed using DSC (trade name: DSC-7, manufactured by Perkin Elmer). 5-10 mg of polyethylene-based resin is inserted into an aluminum pan, placed on the DSC, heated to 230 ° C. at a rate of 80 ° C./min, and left at 230 ° C. for 3 minutes. Thereafter, the temperature is cooled to −10 ° C. at a rate of temperature decrease of 10 ° C./min, and the temperature is increased / decreased from −10 ° C. to 150 ° C. at a rate of temperature increase of 10 ° C./min. The number of endothermic curves observed at the time of temperature increase was evaluated.

~ Disaggregation test ~
0.4 L of water was poured into a household juicer mixer (Tescom Juicer Mixer TM-3-A), and a 10 cm × 10 cm laminate was put therein. After leaving still for 60 minutes, the juicer mixer was switched on and stirred for 3 minutes. After stirring, the laminate was taken out and visually observed.

~ Tensile test ~
In accordance with JIS K6922-2, a tensile test was performed to measure the elongation at break. The test piece was prepared by compression molding. The heating temperature for compression molding was 200 ° C., the heating time was 3 minutes, the pressure was 10 MPa, and the cooling temperature was 30 ° C.

Example 1
[Preparation of modified hectorite]
After adding 60 mL of ethanol and 2.0 mL of 37% concentrated hydrochloric acid to 60 mL of water, 6.55 g (0.022 mol) of N, N-dimethyloctadecylamine was added to the resulting solution and heated to 60 ° C. An N, N-dimethyloctadecylamine hydrochloride solution was prepared. To this solution was added 20 g of hectorite. The suspension was stirred at 60 ° C. for 3 hours, the supernatant was removed, and then washed with 1 L of 60 ° C. water. Then, it dried at 60 degreeC and 10 < ^-3 > torr for 24 hours, and the modified | denatured hectorite with an average particle diameter of 5.2 micrometers was obtained by grind | pulverizing with a jet mill. As a result of elemental analysis, the amount of ions per gram of modified hectorite was 0.85 mmol.

[Preparation of catalyst for macromonomer production]
8.0 g of the above modified hectorite is suspended in 29 mL of hexane, 46 mL of hexane solution of triisobutylaluminum (0.714M) is added, and the mixture is stirred for 1 hour at room temperature, whereby contact formation of the modified hectorite and triisobutylaluminum occurs. I got a thing. On the other hand, 14.0 mg (40 μmol) of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride dissolved in toluene was added and stirred overnight at room temperature to obtain a catalyst slurry (100 g / L). .

[Manufacture of macromonomer]
To a 10 L autoclave, 6,000 mL of hexane and 5 mL of a hexane solution of triisobutylaluminum (0.714 mol / L) were introduced, and the internal temperature of the autoclave was raised to 90 ° C. To this autoclave, 25 mL of the catalyst slurry prepared in [Preparation of catalyst for producing macromonomer] was added, and ethylene was introduced until the partial pressure reached 1.2 MPa to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure was kept at 1.2 MPa. The polymerization temperature was controlled at 90 ° C. 16 minutes after the start of the polymerization, the internal temperature was lowered to 50 ° C. and the internal pressure of the autoclave was depressurized to 0.1 MPa, and then nitrogen was introduced into the autoclave until the pressure became 0.6 MPa and depressurized. This operation was repeated 5 times. The _Mn of the macromonomer extracted from the autoclave is 9,600 and _Mw / _Mn is 2.30. When the terminal structure of the macromonomer is analyzed by ¹³ C-NMR, the number of vinyl terminals and the number of saturated terminals are determined. The ratio (Z) was Z = 0.57. In ¹³ C-NMR, 0.52 methyl branches per 1,000 carbon atoms and 1.22 ethyl branches per 1,000 carbon atoms were detected. Furthermore, long chain branching was not detected in ¹³ C-NMR.

[Production of polyethylene]
To a 10 L autoclave containing the macromonomer produced above, 5 mL of a hexane solution of triisobutylaluminum (0.714 mol / L) and 100 μmol of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride are introduced, The internal temperature of the autoclave was raised to 85 ° C. Ethylene was introduced until the partial pressure reached 0.1 MPa to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure was maintained at 0.1 MPa. The polymerization temperature was controlled at 85 ° C. 75 minutes after the start of the polymerization, the internal pressure of the autoclave was released, and then the contents were suction filtered. After drying, 805 g of polymer was obtained. The obtained polyethylene had an MFR of 53 g / 10 min, a density of 972 kg / m ³ , M _w of 4.1 × 10 ⁴ , M _w / M _n of 3.7, and the number of long chain branches of 0.03 / 1. 1,000 carbons. Other physical properties are shown in Tables 1-3.

The obtained polyethylene and a commercially available polyethylene wax (manufactured by Mitsui Chemicals, high wax 410P, viscosity average molecular weight 4,000) are dry blended at a ratio of 85:15 (polyethylene: wax, weight%) It melt-mixed with the 50 mm single screw extruder made from Plako. The barrel temperatures were C1 / 100 ° C, C2 / 150 ° C, C3 / 180 ° C, C4 / 180 ° C, and die head / 180 ° C. A compression test was performed using the obtained mixture to prepare a test piece, and then a tensile test was performed. Separately from this, MFR at 190 ° C. was measured. Furthermore, extrusion lamination molding was performed with a 25 mm single screw extruder equipped with a T die having a die opening length of 300 mm. The resin temperature was 320 ° C., the base material was kraft paper, the base material feed speed was 100 m / min, and the air gap was 80 mm. The substrate surface was subjected to corona treatment in-line under the condition of 50 W · min / m ² . A disaggregation test was carried out using the obtained laminate.

Example 2
Instead of the polyethylene wax used in Example 1, an ethylene / vinyl acetate copolymer wax (manufactured by Tosoh Co., Ltd., ultra-low molecular weight Ultrasen 7A55A, number average molecular weight 2,500) was used in the same manner. A composition was obtained and various tests were performed.

Comparative Example 1
A mixture was obtained in the same manner using a commercially available high-density polyethylene (Nipolon Hard # 2000, manufactured by Tosoh Corporation, MFR = 15 g / 10 min, density 960 kg / m ³ ) instead of the polyethylene used in Example 1. , Melt tension, MFR, and tensile tests were performed. Moreover, although extrusion lamination molding was tried, the molten film was not stable and a laminate could not be obtained.

Comparative Example 2
50% by weight of commercially available high-density polyethylene (Nipolon Hard # 2500, manufactured by Tosoh Corporation, MFR = 8 g / 10 min, density 961 kg / m ³ ) and low-density polyethylene (Petrocene 203, manufactured by Tosoh Corporation, MFR = 8 g / 10 minutes, density 919 kg / m ³ ) 50% by weight was mixed, and a mixture was obtained in the same manner as in Example 1 except that it was used in place of the polyethylene used in Example 1, and various tests were performed. The results are shown in Table 4, which shows that the disaggregation is poor.

Comparative Example 3
A commercially available low density polyethylene (Petrocene 203, manufactured by Tosoh Corporation, MFR = 8 g / 10 min, density 919 kg / m ³ ) was used in the same manner as in Example 1 except that it was used in place of the polyethylene used in Example 1. A mixture was obtained and various tests were performed. The results are shown in Table 4, which shows that the disaggregation is poor.

Comparative Example 4
Example except that commercially available metallocene linear low density polyethylene (affinity PT1450, manufactured by Dow Chemical Co., MFR = 7.5 g / 10 min, density 902 kg / m ³ ) was used instead of the polyethylene used in Example 1. The mixture was obtained by the same method as 1, and various tests were implemented. The results are shown in Table 4, which shows that the disaggregation is poor.

Comparative Example 5
Various tests were performed in the same manner except that no wax was mixed in Example 1. The results are shown in Table 4, which shows that the disaggregation is poor.

Comparative Example 6
In Example 1, a molding process was attempted without mixing polyethylene, but film formation was impossible.

Comparative Example 7
In Example 2, an attempt was made to perform molding without mixing polyethylene, but it was impossible to form a film.

Claims (4)

Polyethylene-based resin (A) satisfying the following requirements (a) to (d): 99.9 to 50% by weight and polyolefin-based wax (B) 0.1 satisfying any of the following requirements (e) to (g) A polyolefin-based resin composition comprising -50% by weight.
(A) The density is 890 kg / m ³ or more and 980 kg / m ³ or less,
(B) The number of long chain branches having 6 or more carbon atoms is 0.01 to 3 per 1,000 carbon atoms,
(C) Melt tension (MS ₁₉₀ ) (mN) measured at 190 ° C. and MFR (g / 10 min, 190 ° C.) with a load of 2.16 kg are expressed by the following formula (1)
MS ₁₉₀ > 22 × MFR ^−0.88 (1)
The melt tension (MS ₁₆₀ ) (mN) measured at 160 ° C. and the MFR (g / 10 min, 190 ° C.) with a load of 2.16 kg satisfy the following formula (2),
MS ₁₆₀ > 110-110 × log (MFR) (2)
(D) The peak of the endothermic curve obtained in the temperature rise measurement with a differential scanning calorimeter is one. (E) The number average molecular weight (M _n ) measured by gel permeation chromatography is 100 or more and 10,000 or less,
(F) The weight average molecular weight (M _w ) measured by gel permeation chromatography is 200 or more and 20,000 or less,
(G) The viscosity average molecular weight (M _h ) measured by the viscosity method is 200 or more and 20,000 or less. An ethylene polymer having a vinyl group at a terminal obtained by polymerizing ethylene, or an ethylene copolymer having a vinyl group at a terminal obtained by copolymerizing ethylene and an olefin having 3 or more carbon atoms;
(H) M _n is 2,000 or more,
(I) Use of a polyethylene-based resin (A) obtained by polymerizing ethylene and optionally an olefin having 3 or more carbon atoms in the presence of a macromonomer having M _w / M _n of 2 or more and 5 or less. The polyolefin resin composition according to claim 1. The polyolefin resin composition according to claim 1 or 2, wherein the following requirements (j) and (k) are satisfied.
(J) MFR of 190 ° C. and 2.16 kg load is 30 g / 10 min or more and 180 g / 10 min or less,
(K) Tensile breaking elongation measured by JIS K6922-2 is 10% or less An easily disintegratable moisture-proof paper obtained by using paper as a base material and extrusion laminating the polyolefin resin composition according to claim 1.